US4039635A - Soil fungicidal phosphorothioate - Google Patents

Soil fungicidal phosphorothioate Download PDF

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Publication number
US4039635A
US4039635A US05/642,716 US64271675A US4039635A US 4039635 A US4039635 A US 4039635A US 64271675 A US64271675 A US 64271675A US 4039635 A US4039635 A US 4039635A
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Prior art keywords
compound
soil
phosphorothioate
parts
formula
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US05/642,716
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Inventor
Toshiro Kato
Mitsuru Sasaki
Tadashi Ooishi
Kunio Mujai
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals

Definitions

  • This invention relates to a novel organic phosphoric acid ester compound represented by the formula, ##STR2## wherein R 1 is a chlorine or bromine atom, R 2 is a methyl or ethyl group and R 3 is a chlorine or bromine atom or nitro group; to a process for preparing the same; and to a soil fungicide containing said compound as an active ingredient.
  • Plant diseases derived from plant pathogenic fungi which exist in soil to give great damage to agricultural and horticultural crops by infection, have heretofore been feared as a kind of the most difficultly controllable diseases. Although several soil fungicides are being actually used to control said diseases, these fungicides have no sufficient controlling effects.
  • the present inventors conducted extensive examinations from various viewpoints on organic phosphoric acid ester compounds. As the result, the inventors have been successful in developing entirely novel soil fungicides which show sufficient controlling effects, are markedly less toxic to mammals and fishes, show no phytotoxicity to crops and do not remain in crops.
  • the compounds of the present invention have markedly excellent controlling effects on substantially all of soil-borne plant diseases such as damping-off, "Bakanae” disease and sheath blight of rice plants, damping-off of seedlings, and damping-off, Fusarium wilts, yellows, Verticillium wilts, southern blight, rot, late blight of agricultural and horicultural crops.
  • the compounds have actions to promote the spread of root portions of crops to make the growth of the crops vigorous, and particularly show prominent effects against damping-off of seedlings and foot rot of crops which are diseases derived from fungi belonging to the genus Rhizoctonia. It is needless to say that they have no phytotoxicity on every crop.
  • the compounds of the present invention are extremely low in toxicity to warm-blooded animals such as mice, rats, dogs and chickens, and fishes such as carps and gold-fishes. Furthermore, the compounds scarcely remain in crops.
  • the compounds of the present invention are ideal soil fungicides capable of promoting the growth of agricultural crops without causing any environmental pollution.
  • the present inventors sufficiently examined in detail the soil-borne disease-controlling effects of many organic phosphoric acid ester compounds, but no effects of controlling soil-borne diseases could be seen even in those which were quite similar in structure to the present compounds.
  • the present compounds can be prepared with ease and in high yields by reacting a 2,4,6-trisubstituted phenol represented by the formula, ##STR3## wherein R 1 is a chlorine or bormine atom; M is a hydrogen atom, an alkali metal or an ammonium group; R 2 is a methyl or ethyl group and R 3 is a chlorine or bromine atom or nitro group, with O,O-dimethylthiophosphoryl chloride preferably in the presence of an acid binding agent and in the presence or absence of a catalyst such as cupper powder and cuprous chloride, or by reacting a salt of said 2,4,6-trisubstituted phenol with O,O-dimethylthiophosphoryl chloride.
  • R 1 is a chlorine or bormine atom
  • M is a hydrogen atom, an alkali metal or an ammonium group
  • R 2 is a methyl or ethyl group
  • R 3 is a chlorine or bromine atom or nitro
  • an inert organic solvent which may be any of, for example, aliphatic or aromatic hydrocarbons (including halides) such as benzene, toluene and chloroform; ethers such as diethyl ether, dioxane and tetrahydrofuran; and aliphatic alcohols and ketones such as methanol, acetone and methylisobutylketone.
  • the acid binding agent examples include sodium hydroxide; potassium hydroxide; alkali metal carbonates and bicarbonates such as potassium carbonate and sodium carbonate; sodium or potassium methylates and ethylates; and aliphatic, aromatic or heterocyclic tertiary bases such as pyridine, triethylamine and N,N-diethylaniline.
  • the said reaction may be effected by converting the aforesaid 2,4,6-trisubstituted phenol into a salt, preferably an alkali metal or ammonium salt, and then reacting the said salt with O,O-dimethylthiophosphoryl chloride.
  • a salt preferably an alkali metal or ammonium salt
  • reaction scheme 1 Each of the above-mentioned reactions may be carried out at a temperature in a considerably broad range, but is ordinarily effected at 20° to 110° C., preferably 70° to 100° C. in atmospheric pressure.
  • the reactions may be represented by the following reaction scheme 1:
  • the present compounds may be prepared by reacting the aforesaid 2,4,6-trisubstituted phenol with phosphorus trichloride at an elevated temperature in the presence of an acid binding agent and an inert solvent, and then with thiophosphoryl trichloride at about room temperature in the presence of an inert solvent to form a 2,4,6-trisubstituted phenyl thiophosphoryl dichloride, and then reacting the said dichloride with sodium or potassium methylate, or with methanol in the presence of an acid binding agent, in the presence of an inert solvent at a temperature ranging from room temperature to the boiling point of the solvent.
  • This reaction may be represented by the following reaction scheme 2:
  • the present compounds may be obtained also by reacting the aforesaid 2,4,6-trisubstituted phenol with thiophosphoryl trichloride in the presence of an acid binding agent under cooling conditions to form a dichloride, and then reacting the said dichloride with sodium or potassium methylate, or with methanol in the presence of an acid binding agent, in the presence of an inert solvent at a temperature ranging from room temperature to the boiling point of the solvent.
  • This reaction may be represented by the following reaction scheme 3:
  • the present compounds may be used as they are or in the form of any conventional preparations such as granules, dusts, fine granules, wettable powders and emulsifiable concentrates.
  • the present compounds may be contained as active ingredients in an amount of 0.1 to about 90%, preferably 5 to 60%. It is desirable that these preparations are used properly according to their application purposes.
  • the preparations may be applied by any such procedure as sprinkling, dusting, spraying, granule-sprinkling, soil-mixing, injection, irrigation, seed dressing and dipping, and prominent fungicidal effects of the preparations can be displayed by adoption of suitable application procedure.
  • any of solid carriers, liquid carriers and emulsifiers there may be used any of solid carriers, liquid carriers and emulsifiers.
  • the solid carriers include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite and slaked lime
  • examples of the liquid carriers include benzene, alcohols, acetone, xylene, dioxane, methylnaphthalene and cyclohexanone
  • examples of the emulsifiers include alkyl sulfuric acid esters, alkyl sulfonates, aryl sulfonates, polyethylene glycol ethers and polyhydric alcohol esters.
  • the present compounds can be used in admixture also with fungicides other than those mentioned above, insecticides, nematocides, herbicides and fertilizers, and the resulting compositions can greatly contribute to the simultaneous control of diesases and injurious insects and to the promotion of growth of crops.
  • This solid was recrystallized from n-hexane to obtain 18.0 g. of white crystals of O,O-dimethyl O-2-bromo-4-methyl-6-chlorophenyl phosphorothioate having a melting point of 73° to 74° C.
  • the Glauber's salt was separated by filtration and the toluene was removed by distillation, whereby a solid residue was formed.
  • This residue was subjected to fractionation to collect 25.0 g. of fractions having a boiling point of 90° to 92° C. at 0.01 mmHg.
  • 8.7 g. of sodium methylate was gradually added at 20° to 25° C. After stirring at 20° to 25° C. for 3 hours, the reaction liquid was charged with water to separate the liquid into water and toluene layers. The toluene layer was dried with Glauber's salt.
  • This solid was recrystallized from n-hexane to obtain 20.5 g. of white crystals of O,O-dimethyl O- 2-bromo-4-methyl-6-nitrophenyl phosphorothioate having a melting point of 73° to 74° C.
  • the Glauber's salt was separated by filtration and the toluene was removed by distillation, whereby a solid residue was formed.
  • This residue was subjected to fractionation to collect 25.0 g. of fractions having a boiling point of 100° to 102° C. at 0.01 mmHg.
  • 8.7 g. of sodium methylate was gradually added at 20° to 25° C.
  • the reaction liquid was charged with water to separate the liquid into water and toluene layers.
  • the toluene layer was dried with Glauber's salt.
  • a mixture comprising 10 parts of the present compound (1) and 90 parts of clay was sufficiently pulverized to obtain a dust containing 10% of active ingredient.
  • the dust was dusted as it was or thoroughly kneaded with soil.
  • a mixture comprising 50 parts of the present compound (4), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth was sufficiently pulverized to obtain a wettable powder containing 50% of active ingredient.
  • the wettable powder was diluted with water, and the resulting dilution was irrigated into water.
  • a mixture comprising 20 parts of the present compound (3), 60 parts of xylene and 20 parts of an emulsifier (polyoxyethylene phenylphenol polymer type) was sufficiently kneaded to obtain an emulsifiable concentrate containing 20% of active ingredient.
  • the concentrate was diluted with water, and the resulting emulsion was irrigated into soil.
  • a mixture comprising 10 parts of the present compound (5), 85 parts of silica powder, 4.95 parts of calcium lignin sulfate and 0.05 parts of sodium alkylbenzenesulfonate was sufficiently pulverized, kneaded with water, granulated, and then dried to obtain a granule containing 10% of active ingredient. In application, the granule was sprinkled as it was or kneaded with soil.
  • a mixture comprising 2 parts of the present compound (1), 3 parts of N-trichloromethylthio tetrahydrophthalimide and 95 parts of talc was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (6), 3 parts of sodium paradimethylaminophenyl diazosulfonate and 95 parts of clay was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (4), 3 parts of 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole and 95 parts of clay was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (1), 1 part of 5-methyl-3-hydroxy-1,2-oxazole and 97 parts of clay was sufficiently pulverized to obtain a compounded dust containing 3% of active ingredient.
  • a mixture comprising 2 parts of the present compound (5), 8 parts of 1,4-dichloro-2,5-dimethoxybenzene and 90 parts of clay was sufficiently pulverized to obtain a compounded dust containing 10% of active ingredient.
  • a mixture comprising 10 parts of the present compound (7) and 90 parts of clay was sufficiently pulverized to obtain a dust containing 10% of active ingredient.
  • the dust was dusted as it was or thoroughly kneaded with soil.
  • a mixture comprising 50 parts of the present compound (8), 5 parts of a wetting agent (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth was sufficiently pulverized to obtain a wettable powder containing 50% of active ingredient.
  • the wettable powder was diluted with water, and the resulting dilution was irrigated into water.
  • a mixture comprising 20 parts of the present compound (7), 60 parts of xylene and 20 parts of an emulsifier (polyoxyethylene phenylphenol polymer type) was sufficiently kneaded to obtain an emulsifiable concentrate containing 20% of active ingredient.
  • the concentrate was diluted with water, and the resulting emulsion was irrigated into soil.
  • a mixture comprising 10 parts of the present compound (7), 85 parts of silica powder, 4.95 parts of calcium lignin sulfate and 0.05 part of sodium alkylbenzenesulfonate was sufficiently pulverized, kneaded with water, granulated, and then dried to obtain a granule containing 10% of active ingredient. In application, the granule was sprinkled as it was or kneaded with soil.
  • a mixture comprising 2 parts of the present compound (8), 3 parts of N-trichloromethylthio tetrahydrophthalimide and 95 parts of talc was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (8), 3 parts of sodium paradimethylaminophenyl diazosulfonate and 95 parts of clay was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (7), 3 parts of 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole and 95 parts of clay was sufficiently pulverized to obtain a compounded dust containing 5% of active ingredient.
  • a mixture comprising 2 parts of the present compound (7), 1 part of 5-methyl-3-hydroxy-1,2-oxazole and 97 parts of clay was sufficiently pulverized to obtain a compounded dust containing 3% of active ingredient.
  • a mixture comprising 2 parts of the present compound (7), 8 parts of 1,4-dichloro-2,5-dimethoxybenzene and 90 parts of clay was sufficiently pulverized to obtain a compounded dust containing 10% of active ingredient.
  • test results are described below with reference to test examples, but the test examples are part of typical tests, and it is needless to say that the present compounds have extremely broad application scopes as soil fungicides.
  • Farm soil was filled in 9 cm-diameter flower pots. On the surface of said soil was uniformly spread and inoculated 10 ml. per pot of pathogenic soil in which Rhizoctonia solani had been cultured. Subsequently, each of aqueous dilutions of test chemicals in the form of emulsifiable concentrates was irrigated into the thus treated soil in a proportion of 15 ml. per pot. After 2 hours, 10 seeds per pot of cucumber (variety: Kaga-Aonagafushinari) were sowed in soil and, 5 days thereafter, the disease severity of cucumber seedlings was investigated to calculate the percentage of healthy seedlings. The said percentage was calculated according to the following formula: ##EQU1##
  • Farm soil was filled in plastic-made vats of 0.1 m 2 in size. On the surface of said soil was uniformly spread and inoculated pathogenic soil in which Rhizoctonia solani had been cultured, and the pathogenic soil was sufficiently mixed with the farm soil to a depth of 3 to 5 cm from its surface. Subsequently, each of aqueous dilutions of test chemicals in the form of emulsifiable concentrates was irrigated into the thus treated soil in a proportion of 300 ml. per vat.
  • Farm soil was filled in plastic-made vats of 0.1 m 2 in size. Subsequently, pathogenic soil, in which Fusarium oxysporum f. raphani had been cultured, was mixed with and inoculated into the farm soil to a depth of 5 cm. from the surface thereof. On the thus treated soil, 30 seeds per pot of Japanese raddish (variety: Wase 40-nichi) were sowed, and the seeds were covered with soil. After 3 hours, each of aqueous dilutions of test chemicals in the form of emulsifiable concentrates was irrigated into the soil in a proportion of 300 ml. per vat.
  • test compounds in the form of emulsifiable concentrates was diluted with water and applied to rice plants, which had been cultured in pots of 9 cm. in diameter and grown up to 50-60 cm. in height, in a proportion of 10 ml. of the dilution per pot. After 3 hours, a mycelium-discinoculum of Pellicularia sasakii was applied onto the sheaths. 5 Days thereafter, the infectious state of the sheaths was observed, and the degree of damage was calculated according to the following equation: ##EQU2## wherein the infection index was determined on the basis of the following criteria:
  • Farm soil was filled in 11 cm.-diameter flower pots. On the surface of said soil was uniformly spread and inoculated 3 g. per pot of pathogenic soil in which Corticium rolfsii had been cultured for 9 days. Subsequently, each of aqueous dilutions of test chemicals in the form of emulsifiable concentrates was irrigated into the thus treated soil in a proportion of 38 ml. per pot. After 2 hours, 5 seeds per pot of Kidney bean (variety: Nagauzura) were sowed in the soil and, 20 days thereafter, the disease severity of Kidney bean seedlings was investigated to calculate the percentage of healthy seedlings. The said percentage was calculated according to the following formula: ##EQU3##

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Molecular Biology (AREA)
  • Agronomy & Crop Science (AREA)
  • Biochemistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US05/642,716 1975-01-29 1975-12-22 Soil fungicidal phosphorothioate Expired - Lifetime US4039635A (en)

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JA50-12789 1975-01-29
JP1278975A JPS5417804B2 (US20090163788A1-20090625-C00002.png) 1975-01-29 1975-01-29

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JP (1) JPS5417804B2 (US20090163788A1-20090625-C00002.png)
CH (1) CH619714A5 (US20090163788A1-20090625-C00002.png)
CS (1) CS188261B2 (US20090163788A1-20090625-C00002.png)
DK (1) DK142421B (US20090163788A1-20090625-C00002.png)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0141553A1 (en) * 1983-10-21 1985-05-15 Sumitomo Chemical Company, Limited A controlling agent for wood rotting fungi
US4536498A (en) * 1982-12-15 1985-08-20 Sumitomo Chemical Company, Limited Fungicidal composition
US4628049A (en) * 1983-05-13 1986-12-09 Sumitomo Chemical Company, Limited Fungicidal composition comprising a synergistic mixture of a cycloimide fungicide and tolclofos-methyl
US4684634A (en) * 1983-11-01 1987-08-04 Sumitomo Chemical Company, Limited Agricultural and horticultural fungicidal composition
US4820699A (en) * 1987-10-13 1989-04-11 Sandoz, Ltd. Novel bactericidal use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599512A (en) * 1950-04-21 1952-06-03 Dow Chemical Co O-2, 4, 6-trichlorophenyl o, o-dialkylthiophosphates
US3107245A (en) * 1961-08-28 1963-10-15 Geigy Chem Corp Process for the preparation of phosphoric acid esters
US3322864A (en) * 1962-08-14 1967-05-30 Bayer Ag Thionophosphoric acid esters
US3792132A (en) * 1970-12-21 1974-02-12 Stauffer Chemical Co Process for preparing alkyl phenyl phosphate and phosphorothionate compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599512A (en) * 1950-04-21 1952-06-03 Dow Chemical Co O-2, 4, 6-trichlorophenyl o, o-dialkylthiophosphates
US3107245A (en) * 1961-08-28 1963-10-15 Geigy Chem Corp Process for the preparation of phosphoric acid esters
US3322864A (en) * 1962-08-14 1967-05-30 Bayer Ag Thionophosphoric acid esters
US3792132A (en) * 1970-12-21 1974-02-12 Stauffer Chemical Co Process for preparing alkyl phenyl phosphate and phosphorothionate compounds

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536498A (en) * 1982-12-15 1985-08-20 Sumitomo Chemical Company, Limited Fungicidal composition
US4628049A (en) * 1983-05-13 1986-12-09 Sumitomo Chemical Company, Limited Fungicidal composition comprising a synergistic mixture of a cycloimide fungicide and tolclofos-methyl
EP0141553A1 (en) * 1983-10-21 1985-05-15 Sumitomo Chemical Company, Limited A controlling agent for wood rotting fungi
US4612307A (en) * 1983-10-21 1986-09-16 Sumitomo Chemical Company, Limited Controlling agent for wood rotting fungi
US4684634A (en) * 1983-11-01 1987-08-04 Sumitomo Chemical Company, Limited Agricultural and horticultural fungicidal composition
US4820699A (en) * 1987-10-13 1989-04-11 Sandoz, Ltd. Novel bactericidal use

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JPS5188640A (US20090163788A1-20090625-C00002.png) 1976-08-03
DK142421B (da) 1980-10-27
CS188261B2 (en) 1979-02-28
CH619714A5 (en) 1980-10-15
JPS5417804B2 (US20090163788A1-20090625-C00002.png) 1979-07-03
DK578175A (US20090163788A1-20090625-C00002.png) 1976-07-30
DK142421C (US20090163788A1-20090625-C00002.png) 1981-03-23

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